Process of producing fast dyeings



Patented Mar. 24, 1942 U ITED; STATES PATENT Q F E',

PROCESS OF PRODUCING FAST DYEINGS ANDTHE BY FIBER OBTAINED THERE- ErichFischer and Walter Gmelin, Bad Soden in Taunus, and Werner Kirst,Konigstein in Taunus, Germany, asslgnors to General Aniline & FilmCorporation, New York, N. .Y., a corpo-" ration of Delaware No Drawing.Application November 21, 1940, serial No. 367,379. In Germany July 24,1939 g f 8 Claims. The present invention relates to a process oiproducing fast dyeings on cellulose fibers or mix-. tures of cellulosefibers with animal fibers, and

to the dyed fiber obtained thereby.

We have found that drains of very good properties of i'astness may beobtained 'on cellulose fibers or mixtures of cellulose fibers withanimal fibers, for instance: staple fiber from I thus obtained to atreatment with an agent,

yielding metal.

The'tollowin'g examples serve \to illustrate the invention, but they arenot intended to' limit it thereto:

, (1) 1 kilo of a mixed fabric made from 50 parts of wool and 50 partsoistaple fiber from viscose I is dyed for one hour at 95 C. in a bathcontaining 40 grams of thegazo-dyestufl. obtainable by couplingdiazotized 1-(4-amino-benzoylamino) 4-hydroxybenzene-3-carboxylic acidwith 1-(3'- aminophenyl) -5-pyrazolone-3-carboxylic acid, 40 grams ofammonium sulfate, and

600 grams'orsodium sulfate in 30 liters of water..

The temperature is allowed to fall to 80 C. within30 to 45 minutes,whereuponthe material is rinsed and treated for half an hour in the coldwith a solution containing 25 grams of sodium nitrite,

grams of sodium 'dibutylnaphthalenesulionate and '75 cc. oi hydrochloricacid of 2i)"v B6. in

} 3i) liters of cold water.

,The dyestufl is then developed for ha l an hour in a bath containing 75cc. of ammonia of per cent strength and 5 grams of the product obtainedby condensation of 1 moi of octodecyl alcohol with 20 mols of ethyleneoxide in '5 liters oi cold water.

The material is then after-treated for one h at 90 'C. with a solutioncontaining 2 0 1 grams of chromic fluoride,

10 10 grams of glacial acetic acid and i 5 grams of the product obtainedby condensation. of 1 mol of octodecyl alcohol with 20 mole ethyleneoxide in 30 liters of water,v 1

rinsed and dried. A g olden yellow dyeing oi 800d properties ofiastnessis obtained.

(2) 1 kilo of a mixture from 50 parts of wool and 50 parts of staplefiber from viscose is treated for one hour at 95 C. in a solutioncontaining 40 grams of the azo-dyestufi oi the following constitution:

(obtainable by coupling 1 molof 4.4'-bis- [5-oxo- 3-methyl A pyrazolinyl-(1) ]-stllbene-2.2-disulfonic acid which may be obtained from 4.4-dihydrazino-stilbene-2.2'-disulfonlo acid. and

acetoacetic ester, with 1 mol of dlazotized 1- aminobenzene-Z-carboxylicacidandl mol of diazotized l-amino-4-nitrobenzene and reducing thenitro-group to the aminogroup),

40 10 grams of the product obtained by condensation or 1 .mol oioctodecyl alcohol with 20 mole of ethylene oxide and l i 80 grams ofammonium sulfate in 3o liters of water.

600 grams of sodium sulfate are then added and the materiaiisallowed tostand for .45 minutes.

atja temperature ialling to 10 C. rinsed and fur-- ther treated. in themanner indicated in Example 1. A yellow .dyeing or good properties offastness is obtained.

(3) 1 kilo oia mixture of 50 parts of wool and 50 parts oi. staple'fiberfrom viscose is dyed i'or '45 minutes at C.. in a bath containing I ingconstitution:

CH: C H:

3 Dell 4 l l C} 110 H i NH:

(obtainable by coupling diazotized l-l' -nitroe The material is thenallowed to stand for 45 benzoylamino] -4-aminobenzene-3-sulfonic acidminutes at a temperature falling to 70 C., rinsed with 1-[2'-hydroxy-3'-carboxy-5'-sulfophenylland further treated for half anhour in the cold 3-methyl-5-pyrazolone, reducing the nitro-group with tothe amino-group, further diazotizing the ami- 15 no-monoazo-dyestufi?obtained and coupling it 25 grams ofisodPlm f m with 1 [3' aminopheny1]3 methy1 5 pyrazm 1O grgms of sodium d1butylnaphthalenesulfonate lone),an

5 h hl f 20 grams of the product obtained by condensa- 2 m g: gglz oneacld o B in tion of 1 mol of octodecyl alcohol with 20 mols of ethyleneoxide, and the dyestufi is developed for half an hour 40 grams ofammonium sulfate and in a t containing 600 grams of sodium sulfate in 30liters of water. '75 cc. of ammonia of 25'per cent strength and I Thematerial is allowecl to stand for 45 minutes 5 grams of the productobtamed condensatmn at a temperature falling to C" rinsed, diazm of 1mol of octodecyl alcohol with 20 mols of tized, developed andafter-chromed in the manethylene oxide in ner indicated in Example 1.liters of cold wateris g igfig ng 0 good properties of fastness Thematerial is then after-treated for one hour (4) 1 kilo of a mixture of50 parts of wool and at with a solution containing 50 parts of staplefiber from viscose is dyed for 20 o grams of chromic fluoride, 45minutes at 90 C. in a bath containing. 10 grams of glacial acetic acidand r 30 grams o t y fi described in 5 grams of the product obtained bycondensation ample 3,

30 grams of the azo-dyestufi: l-amino-5-hydroxy-naphthalene-"l-sulfonieacid l-aminonaphthalene-'l-sulfonic acid l-amino-nap'nof 1 mole!octodecyl alcohol with 20 mols of ethylene oxide in 30 liters of water,

thalene-7-sulfonic acid, rinsed d dried 10 grams 'of the productobtained by condensa- A brown dyeing of good Properties of fastness tionof 1" mol of 'octodecyl alcohol with 20 rnols is Obtainedp of ethylene iI a- The following table indicates the shades of a. grams f amm ium lfatand number 0! other dyeings obtainable by this in- 600 grams of sodiumsulfate in 'vention:

30 liters of water.

Patent oompment Shade oi the dyeing treated with metal salts on mixturesof wool and artificial silk staple fiber- (obtainable by coupling 1 molof 4.4'-bis-[5-oxo-3-metlgl-A'-pymzolln l-(1)]-etilbene-2.2'- disulionicacid (see Example 2) with 1 mol 0! diam zed l-amino-4- ydroxybenzene-B-carboxylic. acid and l min] or diazotizedl-amino-2-hydroxy-4-nitrobonzene and reducing the nitro-group to theamino-group).

Treated with chromic fluoride or potassium biehromate: brown.

on, I on. =;N\ I /N=( .3 l 1 2. N=NC=C- c= -N=N.C0.HN on 5 1103s SOaH IH OH NH: 7 00B (obtainable by couplingl mol of the bis-pyrazolone from4.4-bis hydrazino-l.l'-diphenyl- Treated with chromic fluoride orpotassium 2.2-disulfonic acid and aeetoacetie ester with 1 mol ofdiazotized l-amino-Zi-nit'mbenzene bichromate: yellow. and 1 mol ofdiazotized 1-[4'-eminobenzoylaminoH-hydroxybenzeneii-earboxyhc acid andsubsequently reducing the nitro-group to the amino-group).

e I i r Shade of the dyeing treated with metal salts n Pam! mipmnimixtures oi wool and artificial silk staple liber v cm I am C=N\ /N=C rl 3. NH N= -c=c 4 c= -N= N N=N on I H038 80:11 I OH OH C O OH O O H(obtainable by cou link 1 mol oi the bis-pyrazoione from4.4-bis-hydrazino-1. l'- Treated with chromic fluoride or potassium Idipheny1-2.2'-disul onle acid and acetoaeetic ester. with 1 mol oidiaz'otized l-aminobichromate: brown-orange. 4-nitrobenzene-2-carboxylicacid and 1 mol 0! diazotized 4-amino-4'-hydroxy-l.1-

azobenzene-3-carboxylic acid and reducing the nitro-group to theamino-grou 4. 4-amino-l.l'-azobenzene-3-carboxylic aci-y-sulioniciacid1(3'-aminophcnyl)- Treated with ehromic fluoride: orange.

6-pyrazolone-3-carb03llc acid. I 0H v (obtainable by con ling 1 moi ofthe pyrazolone irom the hydrazine oi dehydrothioto- Treated with chromicfluoride: ycllowish-brown. luidinesulionic ac d and acetoacetic ester,with 1 mol oidiazotized I-am no-Z-hydroxy- 4-nitrobenzene and reducingthe nitro-group to the amino-group).

6. 4-arnino-4'-hydroxs -1.1'-azobenzene-3-mrboxylic acid 1--amino-phenyl)-5- Treated with chromic fluoride: red.

pyrazoionee-carboxyllc acid. I 7

c 0 011 v c 0 or! (obtainable by coupling 1 mol of4.4'-bis-[5-oXc-3-methyl-N-p razolinyl-(i)l-stilbene- Treated withgotassium hichroniate: orange,

2.2'-disulionic acid (see Example 2) with 1 moi of diazotizedl-ammo-a-hydroxybcnzene- I with chromic uoride: yellow. 3-carboxylicacid and l moi oi-diazotized l-arn1no-4-nitrobenzene-2-carboxylic acidand reducing the nitroqzrouptc the amino-grogp). v

. 1 ac: 8. 1-(4'-aminophenyl)-3-methyl-5-pyrazoione2-amino-5-hydroxy-naphthelene-7- Treated with chromic'fluoride: brown.

,1 sulionic acid l-amino-4-hydroxybenzene-3mrboxylic acid.

(obtainable by coupling 2 mols of diazotized5-nitro-2-arniuo-l-hydroxybenzene-Q Treated with copper sulfate:brownish red.

sulionic acid with 1 mol oi the urea irorn1-(4'-amino;iil;enyl)-3-methyl-5-pyrewwne and subsequently reducing thenitro-zroups. or by coup g 1 mol oi dtazotized B'n tro-2-amino-l-hydroxybenzene-4-sulionic acid with 1 moi ofl-(4f-aminophenyD-3-met hyl- 5-pyrazolone, phosgenating and reducing theurea thus obtained).

N=N NH 10 OH Sol-NH SOaH Hons N I v OOH (ob tainablc by coupling thetetrazo-compou nd lrorn 1 mol of para-amino-benzoyl- Treated withchromic fluoride: red. pamphenylenediamineinan acid medium, with lznolof 1- -amino-4'-suliophenyl)- A fi-pyrazolone-ii-carboxylio acid andsubsequently coupling the compound obtained with s 1 mol oi2-(4'-hydroxy-a'mrboxy-phenyl-sul onyl)-amino-5-hydroxy-na h.'thalene-7-sulionlcacid in the presence of sodium carbonate).

We claim: 4 A v I aninial fibers, which comprises applying to the 1. Aprocess of producing iast-" dyeings. on fiber a water-solublepyrazolone-azo-dyestufise- -fibrous material of the group consisting ofcellulected from the group consisting of monoand lose fibers andmixtures oicelluloce fibers with diaazo-dyestufls which contains in themolecule 4- aerate; g at least one amino-group capable-of being diazothe dyeingsthus obtained to a treatment with tized and at least onegrouping capable of forman agentyielding chromium. ing a metal complexcompound, but noihydroxyl 4. A process of producing iast brownish-redgroup rendering coupling possible, then diazodyeings' on fibrousmaterial of the group consisttizing, developing thedyestufl by means oran 1 ing of cellulose fibers and mixtures of cellulose alkalinetreatment and subjecting the 'dyeings fibers withenimal-fibers i h co pise appl thus obtained to a treatment with an agent yielding to the.fiber a water-soluble pyrazolone-azomg metal. 5 dyestufl o! thefollowing constitution: A H v f O NH N N-Q= I on SOzH

2. A process of. producing fast yellow dyeings then diazotizing,developing the dyestufi "by on fibrous material of the group consistingoimeans of an alkaline'treatment-and subjecting cellulose fibers andmixtures of cellulose fibers the dyeings thus obtained to a treatmentwith arr with animal fibers which comprises applying to agent yieldingcopper. j

the fiber a water-soluble pyrazolone-azo-dyestuif 5. Fibrous material ofthe group consisting of of the following constitution:

SOaH

then diazQtiz ing, developing the dyestufl by with animal fibers, dyedwith a water-soluble means of an alkaline treatment and subiecting 'pyralon -a y s uff selected from the grou the dyeings thus obtained to atreatment with an consisting of monoand disazo-dyestufis by thecellulose fibers and mixtures of cellulose fibers agent yieldingchromium. process claimed in claim 1. v

3. A process of producing fast golden-yellow 6. Fibrous material of thegroup consisting of .dyeings on fibrous material of the group consist--cellulose fibers'and mixtures of cellulose fibers ing of cellulosefibers and mixtures of cellulose wi h an mal fibe s, dyed h a Water-solble fibers withanimal fibers, which comprises appy o fl y y the Processa m plying to the fiber a water soluble pyrazolonein cl i l azo-dyestuflof the following constitution: i rous t al of t e oup consisting of PN'Hft p cellulose'fibers and mixtures of cellulose fibers o g withanimal fibers,-dyed with a water-soluble- I pyrazolone-azo-dyestufl bythe process claimed in claim 3 v 8. Fibrous material of the groupconsisting "of N i cellulose fibers and mixtures of cellulose fiberswith animal fibers; dyed with-a water-soluble W V COO'H 5o 7 ERICHFISCHER. I 1 l I s WAL'I'ER-GMEHN. then diazotizmg. developing thedyestufl .by' I WERNER KIRST. means of an alkaline treatment andsubjecting l

